Compositions, which promote plant growth and protect plants based on oxide ethers and oxime esters

ABSTRACT

Novel oxime ethers and oxime esters of the formula I given herein have various advantageous effects with regard to stimulation of plant growth, particularly in the early stage of development of the plant. Furthermore, such compounds have the property of rendering, in the sense of an antidote action, agricultural chemicals which would otherwise damage the plants (phytotoxic chemicals) more compatible with the cultivated plants. Herbicides that are insufficiently selective can be used for example in the presence of such oxime derivatives in specific cultivated crops for combating weeds, without disadvantageous consequences for the cultivated plants.

This is a division of application Ser. No. 129,499 filed on Mar. 11,1980, now U.S. Pat. No. 4,466,822, which is a division of applicationSer. No. 881,953, filed on Feb. 27, 1978, now abandoned.

DETAILED DISCLOSURE

The present invention relates to novel oxime ethers and oxime esters ofthe general formula I ##STR1## to their production, and also to novelcompositions based on these compounds, and to the application of thesecompositions or compounds for promoting plant growth or for protectingcultivated plants.

In the formula I

Ar represents a phenyl group of the formula ##STR2## an α- or β-naphthylgroup, or a heterocyclic ring of the formula ##STR3## X represents --CN,--NO₂, halogen, lower alkanoyl, a carboxylic acid ester group, hydrogen,a carboxylic acid amide group, or lower alkyl.

Q represents lower alkyl which is straight-chain or branched chain, orwhich can be interrupted by hetero atoms or substituted by halogen, orrepresents lower alkenyl or haloalkenyl, lower alkynyl, C₃ -C₇-cycloalkyl optionally substituted by halogen, or represents lowercyanoalkyl, a lower alkanecarboxylic acid ester group, a loweralkanecarboxylic acid amide group, an aliphatic acyl group, anaraliphatic, cycloaliphatic or optionally substituted aromatic orheterocyclic acyl group, alkylsulphonic acid or a sulphonic acid amidegroup,

R₁ represents hydrogen, halogen, lower alkyl, lower alkoxy, or a phenoxygroup which is in the para position and which is optionally substituteda maximum of twice by halogen, --CN, NO₂ or CF₃,

R₂ and R₃ independently of one another represent hydrogen, halogen, NO₂,lower alkyl, halogenoalkyl or lower alkoxy,

R₄ and R₅ independently of one another represent hydrogen, halogen, NO₂or lower alkyl, and

Z represents oxygen or sulphur,

with the proviso that, if Ar represents an unsubstituted phenyl groupand Q represents the radical --CH₂ CN, X represents NO₂, halogen, loweralkanoyl, a carboxylic acid ester group, hydrogen, a carboxylic acidamide group or lower alkyl.

Depending on substitution of these oxime derivatives of the generalformula I, there are obtained products which have various propertiesinfluencing plant growth, and which can be used, in agriculturegenerally or in special areas of plant protection, as plant-growthregulators or alternatively as antidotes (safeners) for pesticides.

By halogen in the formula I is meant fluorine, chlorine, bromine oriodine.

The expression alkyl on its own or as part of a substituent embracesbranched-chain or straight-chain C₁ - to C₈ -alkyl groups; and loweralkyl denotes C₁ -C₄ -alkyl. Examples are methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, as well as thehigher homologues amyl, isoamyl, hexyl, heptyl or octyl, together withtheir isomers. Analogously, alkanoyls or cyanoalkyls contain anadditional C atom. A lower alkanecarboxylic acid ester consists of alower alkyl part having 1-4 C atoms, the carbonyl group and an alcoholicor phenolic radical having 1 to 8 C atoms. To be mentioned in particularare acetic ester --CH₂ --COOT (T=C₁ -C₈ -radical) and 1-propion ester--CH(CH₃)--COOT, with OT=a lower aliphatic alcohol radical beingpreferred in both cases.

Alkenyls denote aliphatic radicals having one or also two double bonds("alkadienyls") and a maximum of 6, preferably 4, C atoms.Halogenoalkenyls contain up to 3 halogen atoms, preferably chlorine orbromine. Lower alkynyl denotes propynyl (-propargyl) and butynyl.

Carboxylic acid amides and sulphonic acid amides embrace alsomonosubstituted or symmetrically or unsymmetrically disubstitutedamides, with the substituents being optionally lower alkyl, loweralkenyl, propynyl or butynyl, and also once a phenyl ring, which can besubstituted or unsubstituted according to the definition for R₂ /R₃.

C₃ -C₇ -cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and cycloheptyl. Cycloaliphatic radicals correspond to thesering systems, but they can also contain, depending on possibility, oneor more double bonds.

An araliphatic radical includes an aryl group, such as phenyl,optionally mono- to trisubstituted according to R₂ /R₃, or naphthyl,fluorenyl, or indanyl, which is bound by way of lower alkyl or loweralkenyl to the radical of the molecule. Examples are the fundamentalsubstances benzyl, phenethyl, phenylallyl, as well as homologues.

Aromatic carboxylic acids, which can form the aromatic acyl groups, arederived from aromatic substances, such as in particular phenyl, and canbe substituted as defined under R₂ /R₃.

Heterocyclic carboxylic acids are derived from mono- or bicyclic ringshaving 1 to 3 identical or different hetero atoms O, S and N. To bementioned are 3- to 6-membered, especially 5- or 6-membered,heterocycles, which can be saturated, partially saturated orunsaturated, and can be optionally substituted as defined under R₄ /R₅.Examples which may be mentioned but which do not constitute anylimitation are: furan, nitrofuran, bromofuran, methylfuran, thiophene,chlorothiophene, pyridine, 2,6-dichloropyridine, pyrimidine, pyridazine,pyrazine, piperidine, methylpiperidine, morpholine, thiomorpholine,tetrahydrofuran, oxazole, pyrazole, pyrrole, pyrroline, pyrrolidine,thiazole, 2,3-dihydro-4H-pyrane, pyrane, dioxane or 1,4-oxathi-(2)-ine.

Examples of aliphatic chains interrupted by hetero atoms aremethoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl,ethylthioethyl, methylaminoethyl, tert-butylaminoethyl oralkoxyalkoxyalkyl, such as methoxyethoxyethyl.

It has been shown that oxime ethers and oxime esters of the formula Ihave for practical purposes extraordinarily advantageous properties forpromoting plant growth, without there being any disadvantageousconsequences for the plants treated therewith. Applied in small dosageamounts, active substances of the formula I have in particular theability to stimulate both the germinating seed and the young plantswhich are developing. With specific dosage amounts, this leads to aclearly enlarged root system, to an increased rate of photosynthesis andto a more rapid development of parts of plants above the soil. Theaction of the oximes of the formula I is however not restricted to theearly stage of plant development, but can be observed also in the caseof later application, or in the case of a partial application tospecific parts of plants (seed dressings, pre-swelling of the seed, roottreatment, treatment of shoots or leaf application). This manner oftreatment leads to a more rapid growth of the treated plant, to improvedfruit setting, to an earlier point of time of ripening and of harvestingand to an increased or otherwise improved crop yield. The activesubstances can be applied to the plant, to parts of the plant, to theseed or to the soil, and the mode of application corresponds tocustomary techniques of application or of dressing. A further veryimportant advantage is the improvement in the power to compete of theplant treated in this manner compared with that of the weed flora whichhas not been growth-stimulated. The active substance of the formula Imust of course be applied in this case to the seed or to the seedlingsof the desired crop of plants and not to the crop area in general. Athird important advantage, which is a result of the greatly expandingroot system of a plant thus treated, is the possibility, even underenvironmental conditions that are not particularly favourable, ofachieving a satisfactory development of the crop of cultivated plantsand thus an adequate crop yield. Examples which may be mentioned of suchdisturbance factors hostile to the environment are: soils low innutrients, drought, low temperatures during the early development of theplant, sudden frosts, and reduced sunlight in consequence of anunfavourable time of the year or of an unfavourable location.

Oxime ethers and oxime esters of the formula I possess however to a verygreat extent properties for regulating plant growth, depending on thepoint of time of application and on the type of plant.

Various other possibilities of application of the oximes of the formulaI may be listed as follows, but they do not constitute a limitation:

application for improved leaf formation in crops of tobacco, cabbage orlettuce, and avoidance of undesirable side shoots;

application for increasing yield in crops of leguminosae (e.g. in cropsof peas, beans, soya beans and peanuts) by promoting generative growth(increase of tillering);

application for increasing the rigidity of crops prone to flattening,such as cereals (prevention of the sagging of plants under unfavourableweather conditions, such as storms or continual rain);

application for facilitating harvesting of fruit by promoting theformation of abscission layers between the fruit and the shoot part ofthe plant; and

application for raising the storage capacity for plant substances(sugar, proteins, oils, and so forth), or for temporarily maintainingthat which has been stored.

The storage capacity for plant substances includes the possibility ofretaining that already stored for longer than under natural conditions.Thus, the storability of potatoes can be improved. Furthermore, thesugar content in sugar cane shortly before harvesting can be keptconstant by application of specific oxime ethers of the formula I,whereby the tendency of the plant to form further side shoots at theexpense of the sugar content is counteracted.

Compositions for influencing plant growth, especially for inhibitinggrowth, have already been described at various times; thus,chlorocholine chloride in particular is suitable for the shortening andstabilising of the stems in wheat crops. According to GermanOffenlegungsschrift No. 2,458,165, bis(p-chlorophenyl)-acetic acid, orsalts, esters amides or nitriles thereof, are said to effect a similarshortening of stems in cereal crops. In German Offenlegungsschrift No.2,407,148, 2,6-disubstituted phenoxyacetates or 2,6-disubstitutedphenoxypropionates are recommended as growth regulators. The mode ofacting of these substances, particularly with low applied amounts andlow concentration, is however not satisfactory. The position is similarin the case of p-chlorophenyldimethylacetic acid (East German PatentSpecification No. 113,890), and also in the case of2-cyano-bicyclo[2,2,1]heptane (French Patent Specification No.2,256,722). As was shown by tests, the action of these compounds is veryunsatisfactory.

The arylglyoxilnitrile oximes, suggested in the U.S. Pat. No. 3,799,757,of the general formula ##STR4## are insufficiently effective as growthinhibitors and plant-growth regulators; they are moreover not stable anddecompose after a fairly short period of time.

Oximes of the formula I surprisingly possess a further very importantproperty. They are excellently suitable for protecting cultivatedplants, such as cultivated millet, rice, maize, varieties of cereals(wheat, rye, barley or oats), cotton, sugar beet, sugar cane, soya bean,etc., against being attacked by agricultural chemicals, particularly byherbicides of the widest variety of classes of substances, such astriazines, phenylurea derivatives, carbamates, thiolcarbamates,halogenoacetanilides, halogenophenoxyacetates, substitutedphenoxyphenoxyacetates and -propionates, substitutedpyridineoxyphenoxyacetates and -propionates, benzoic acid derivatives,etc., in cases where these do not act selectively or not sufficientlyselectively, that is to say, damage to a greater or lesser extent thecultivated planes in addition to the weeds to be combatted. Theinvention relates also to compositions which contain these oxime ethersof the formula I, together with biologically acting additives, such asherbicides, fungicides or insecticides.

Various substances have already been suggested for overcoming thisproblem, which substances are able to specifically antagonise theharmful action of a herbicide on the cultivated plant, i.e. to protectthe cultivated plant without noticeably affecting the herbicidal actionon the weeds to be combatted. Depending on its properties, such anantidote can be used for the preliminary treatment of the seed of thecultivated plant (dressing of the seed or of the seedlings); or it canbe applied into the seed furrows before sowing; or it can be applied asa tank mixture, on its own or together with the herbicide, before orafter emergence of the plants. The treatment with the antidote can becarried out before or after, or simultaneously with, the herbicidaltreatment. The pre-emergence treatment includes both the treatment ofthe cultivated area before sowing (ppi=pre plant incorporation) and thetreatment of the sown cultivated area before emergence of the plants.

Thus, the British Patent Specification No. 1,277,557 describes thetreatment of seed and seedlings of wheat and sorghum with certain estersand amides of oxamic acid before the attack byN-methoxymethyl-2',6'-diethyl-chloroacetanilide (Alachlor). Otherpublications (German Offenlegungsschriften Nos. 1,952,910 and 2,245,471,and French Patent Specification No. 2,021,611) suggest antidotes for thetreatment of cereals, maize seed and rice seed to protect them againstthe attack from herbicidal thiolcarbamates. In German PatentSpecification No. 1,576,676 and U.S. Patent Specification No. 3,131,509,by hydroxyamino-acetanilides and hydantoins are suggested for protectingcereal seeds against carbamates, such as IPC, CIPC, etc.

However, there has not hitherto been suggested in the literature a classof substances which on the one hand are able to impart to plants stronggrowth-stimulating impulses, and on the other hand have the ability toprotect, in the sense of an antidote effect, plants against aggressiveagricultural chemicals.

Compounds of the formula I to be particularly emphasised are thosewherein Ar has the given meaning, and the other substituents have thefollowing meanings:

X represents cyano, nitro, halogen, lower alkanoyl, a carboxylic acidester group of a lower aliphatic alcohol, a carboxylic acid amide group,or lower alkyl,

Q represents lower alkyl which is straight-chain or branched-chain, orwhich can be interrupted by a hetero atom or substituted by halogen, orQ represents lower alkenyl, lower alkynyl, lower cyanoalkyl, a loweralkanecarboxylic acid ester group, a lower alkanecarboxylic acid amidegroup, a lower aliphatic acyl group, a cycloaliphatic acyl group having4 to 6 C atoms, or an unsubstituted sulphonic acid amide group or asulphonic acid amide group mono- or disubstituted by a lower aliphaticradical,

R₁ represents hydrogen, or a phenoxy group in para-position,

R₂ and R₃ independently of one another represent hydrogen, halogen orlower alkyl,

R₄ and R₅ represent hydrogen, and

Z represents oxygen or sulphur.

Preferred compounds amongst these are compounds of the formula 1a##STR5## wherein the substituents have the following meanings: Xrepresents cyano, nitro, halogen, lower alkanoyl, a carboxylic acidester group of a lower aliphatic alcohol, a carboxylic acid amide groupor lower alkyl,

Q represents a lower straight-chain alkyl chain which is interrupted byoxygen, or Q represents lower alkenyl, lower alkynyl, lower cyanoalkyl,a lower alkanecarboxylic acid ester group, a lower alkanecarboxylic acidamide group, a lower aliphatic acyl group, a sulphonic acid amide groupwhich is unsubstituted or is mono- or disubstituted by a lower aliphaticradical,

R₁ represents hydrogen,

R₂ represents hydrogen, halogen, lower alkyl or lower alkoxy, and

R₃ represents hydrogen, halogen, lower alkyl or lower alkoxy.

Particularly preferred compounds of this last-mentioned group are thosecompounds wherein the substituents of the formula Ia have the followingmeanings:

X represents cyano, nitro, halogen, lower alkanoyl, a carboxylic acidester group of a lower alkanol, or a carboxylic acid amide group,

Q represents lower alkynyl, lower cyanoalkyl a lower alkanecarboxylicacid ester group, a lower alkanecarboxylic acid amide group,

R₁ represents hydrogen,

R₂ represents hydrogen, halogen or lower alkyl, and

R₃ represents hydrogen, halogen or lower alkyl.

Preferred compounds within the last-mentioned group are, within narrowerlimits, those compounds wherein the substituents of the formula Ia havethe following meanings:

X represents cyano, chlorine, bromine, acetyl, propionyl, --COOCH₃,--COOC₂ H₅, --CO--NH₂, --CO--NHCH₃ or --CO--N(CH₃)₂,

Q represents propynyl or butynyl, cyanomethyl or cyanoethyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, methoxycarbonylethyl orethoxycarbonylethyl, an acetamide or propionamide group optionallysubstituted on the N atom by one or two lower aliphatic groups,

R₁ represents hydrogen,

R₂ represents hydrogen, halogen or methyl, and

R₃ represents hydrogen, halogen or methyl.

Compounds amongst these which form an important subgroup are thosewherein X represents a cyano group.

Another preferred range of active substances of the formula I whichpromote plant growth and protect plants is that embraced by the formulaII ##STR6## wherein R₁, R₂ and R₃ independently of one another representhydrogen, halogen, NO₂, lower alkyl, halogenoalkyl or lower alkoxy,

X represents --CN, --NO₂, halogen, the acetyl group, a carboxylic acidester group of a lower aliphatic alcohol or a carboxylic acid amidegroup,

n represents 1, 2 or 3,

R₉ represents hydrogen or lower alkyl,

R₁₀ represents --CONH₂, --CO--NH-(lower aliphatic radical),--CO--NH-cycloalkyl, --CONH--(C₆ H_(5-m)) (halogen, lower alkyl)_(m) or--CN, and

m represents an integer, 0, 1, 2 or 3.

Preferred compounds within the compass of the formula II are compoundsof the formula III ##STR7## wherein X' represents --CN, --NO₂, chlorine,acetyl, lower alkoxycarbonyl, allyloxycarbonyl, carbamoyl ordi-lower-alkylcarbamoyl,

R₁₀ represents --CN, --CO--NH₂, --CO--NH-lower alkyl or --CONH(C₆H_(5-m)) (Cl, Br, CH₃)_(m), and

m represents an integer, 0, 1 or 2.

The preferred individual compounds include:

α-cyanobenzylidene-amino-oxacetamide of the formula ##STR8##α-cyanobenzylidene-amino-oxyacetic acid ethyl ester (Comp. 1.4),α-(cyanoethoximino)-benzacetonitrile (Comp. 1.44).

Effective chloroacetanilides, which in some cases are not sufficientlytolerated by cultivated plants, such as cereals, rice, cultivatedsorghum, and so forth, but which, when acting together with the oximeethers of the formula I of the present invention, leave such cultivatedplants unharmed, without losing any of their normal effectivenessagainst weeds, have become known, for example, from the U.S. Pat. Nos.3,547,620, 3,403,994, 3,442,945, 3,637,847, 3,598,859, 3,819,661,3,946,045 and 3,983,174, and from the German Offenlegungsschriften Nos.2,212,268, 2,305,495, 2,328,340, 2,402,983, 2,405,183 and 2,405,479.

The antidotes of the formula I, II or III are used preferably togetherwith herbicidal chloroacetanilides of the formula ##STR9## wherein R₁₁represents lower alkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen,

R₁₂, R₁₃ and R₁₄ independently of one another represent hydrogen, loweralkyl, alkoxy, alkoxyalkyl, trifluoromethyl or halogen, and

R₁₅ represents a C₁ -C₄ -alkyl which is optionally substituted bycarboxy, carboxylic acid ester, carbonamide, or carbonamide substitutedby one or two lower aliphatic radicals, or by --CN; or wherein R₁₅represents propynyl, butynyl, an acetalised carbonyl group,1,3-dioxolan-2-yl-alkyl, 1,3-dioxolan-5-yl-alkyl, 1,3-dioxan-2-yl-alkyl,furanylmethyl, tetrahydrofuranylmethyl, or alkoxyalkyl of the form--A--O--R₁₆, wherein A represents an alkylene chain having 1 to 4 Catoms, of which 1 or 2 belong to the direct chain, and R₁₆ representslower alkyl, alkenyl, or cycloalkyl or cycloalkylmethyl having 3 to 6 Catoms in the ring.

The expressions "lower alkyl" or "lower aliphatic radical" denote groupshaving at most 4 carbon atoms, and correspond to the aforementioneddefinition for the formula I, and likewise the term "halogen".

Some chloroacetanilides which are particularly suitable for use with theantidotes according to the invention are listed below:

N-ethoxymethyl-2-methyl-6-ethyl-chloroacetanilide,

N-methoxymethyl-2,6-diethyl-chloroacetanilide,

N-(2'-methoxyethyl)-2,6-dimethyl-chloroacetanilide,

N-(2'-allyloxyethyl)-2,6-dimethyl-chloroacetanilide,

N-(2'-n-propoxyethyl)-2,6-dimethyl-chloroacetanilide,

N-(2'-isopropoxyethyl)-2,6-dimethyl-chloroacetanilide,

N-(2'-methoxyethyl)-2-methyl-6-ethyl-chloroacetanilide,

N-(2'-methoxyethyl)-2,6-diethyl-chloroacetanilide,

N-(2'-ethoxyethyl)-2-methyl-6-ethyl-chloroacetanilide,

N-[3'-methoxyprop-(2')-yl]-2-methyl-chloroacetanilide,

N-[3'-methoxyprop-(2')-yl]-2,6-dimethyl-chloroacetanilide,

N-[3'-methoxyprop-(2')-yl]-2-methyl-6-ethyl-chloroacetanilide,

N-[3'-methoxyprop-(2')-yl]-2,6-diethyl-chloroacetanilide,

N-(2'-ethoxyethyl)-2,6-diethyl-chloroacetanilide,

N-(2'-n-propoxyethyl)-2-methyl-6-ethyl-chloroacetanilide,

N-(2'-n-propoxyethyl)-2,6-diethyl-chloroacetanilide,

N-(2'-isopropoxyethyl)-2-methyl-6-ethyl-chloroacetanilide,

N-chloroacetyl-2,6-dimethylanilino-acetic acid ethyl ester,

N-chloroacetyl-2,6-diethylanilino-acetic acid ethyl ester,

N-chloroacetyl-2,6-dimethylanilino-acetic acid methyl ester,

N-chloroacetyl-2-methyl-6-ethylanilino-acetic acid isopropyl ester,

2-[N-(α-chloroacetyl)-2,6-dimethylanilino]acetaldehyde-diethylacetal,

N-[3'-methoxyprop-(2')-yl]-2,3-dimethyl-chloroacetanilide,

N-(2'-ethoxyethyl)-2-methyl-chloroacetanilide,

N-(2'-methoxyethyl)-2-methyl-chloroacetanilide,

N-[2'-methoxyprop-(1')-yl]-2,6-dimethyl-chloroacetanilide,

N-[2'-methoxyprop-(1')-yl]-2-methyl-6-ethyl-chloroacetanilide,

N-[3'-ethoxyprop-(2')-yl]-2-methyl-6-ethyl-chloroacetanilide,

N-[1'-methoxybut-(2')-yl]-2,6-dimethyl-chloroacetanilide,

N-(2'-methoxyethyl)-2-methyl-6-methoxy-chloroacetanilide,

N-(n-butoxymethyl)-2-tert.butyl-chloroacetanilide,

N-[3'-ethoxyprop-(2')-yl]-2,6-dimethyl-chloroacetanilide,

N-(2'-methoxyethyl)-2-chloro-6-methyl-chloroacetanilide,

N-(2'-ethoxyethyl)-2-chloro-6-methyl-chloroacetanilide,

N-(2'-ethoxyethyl)-2,3,6-trimethyl-chloroacetanilide,

N-(2'-methoxyethyl)-2,3,6-trimethyl-chloroacetanilide,

N-(2'-isopropoxyethyl)-2,3,6-trimethyl-chloroacetanilide,

N-cyanomethyl-2,6-dimethyl-chloroacetanilide,

N-(but-1-in-3-yl)-chloroacetanilide,

N-propynyl-2-methyl-6-ethyl-chloroacetanilide,

N-(1,3-dioxolan-2-ylmethyl)-2,6-dimethyl-chloroacetanilide,

N-(1,3-dioxolan-2-ylmethyl)-2-ethyl-6-methyl-chloroacetanilide,

N-(1,3-dioxan-2-ylmethyl)-2-methyl-6-ethyl-chloroacetanilide,

N-(2'-furanyl-methyl)-2,6-dimethyl-chloroacetanilide,

N-(2'-furanyl-methyl)-2-chloro-6-methyl-chloroacetanilide,

N-(2'-tetrahydrofuranyl-methyl)-2,6-dimethyl-chloroacetanilide,

N-(N'-propargylcarbamylmethyl)-2,6-dimethyl-chloroacetanilide,

N-(N',N'-dimethylcarbamylmethyl)-2,6-dimethyl-chloroacetanilide,

N-(n-butoxymethyl)-2,6-diethyl-chloroacetanilide,

N-(2'-n-butoxyethyl)-2,6-diethyl-chloroacetanilide,

N-[3'-methoxybut-(2')-yl]-2,6-dimethyl-chloroacetanilide, and

2-chloro-N-isopropylacetanilide.

Suitable herbicidal thiolcarbamates which when used, in crops ofcereals, rice or cultivated sorghum, together with compounds of theformula I, II or III are made more compatible with the crops correspondpreferably to the formula ##STR10## wherein R₁₇ represents lower alkyl,alkenyl, chloroallyl, dichloroallyl, trichloroallyl, benzyl orp-chlorobenzyl,

R₁₈ represents C₂ -C₄ -alkyl, and

R₁₉ represents C₂ -C₄ -alkyl or cyclohexyl, or wherein

R₁₈ and R₁₉ together with the N atom form a hexahydro-1H-azepine ring, adecahydroquinoline ring or a 2-methyl-decahydroquinoline ring.

The following thiolcarbamates may be mentioned as examples of suchcompounds:

S-ethyl-N,N-dipropylthiocarbamate,

S-ethyl-N,N-diisobutylthiocarbamate,

S-2,3-dichloroallyl-N,N-diisopropylthiolcarbamate,

S-propyl-N-butyl-N-ethylthiolcarbamate,

S-2,3,3-trichloroallyl-N,N-diisopropylthiolcarbamate,

S-propyl-N,N-dipropylthiolcarbamate,

S-ethyl-N-ethyl-N-cyclohexylthiolcarbamate,

S-ethyl-N-hexahydro-1H-azepine-1-carbothioate,

S-isopropyl-N,N-hexamethylene-thiolcarbamate,

S-(p-chlorobenzyl)-N,N-diethylthiolcarbamate,

N-ethylthiocarbonyl-cis-decahydroquinoline,

N-propylthiocarbonyl-decahydroquinaldine,

S-ethyl-N,N-bis-(n-butyl)-thiolcarbamate, and

S-tert.butyl-N,N-bis-(n-propyl)-thiolcarbamate.

Further examples of thiolcarbamates that can be used are described inthe U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786and 3,582,314.

The following may be mentioned as further preparations which withcompounds of the formula I can be made more compatible with the crops ofcultivated plants:

α-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid methyl ester,

α-[4-(4-trifluoromethylphenoxy)-phenoxy]-propionic acid methyl ester,

α-[4-(2-chloro-4-trifluoromethylphenoxy)-phenoxy]-propionic acid methylester, and

α-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-propionic acid methyl ester.

The applied amount of antidote varies between about 0.01 and about 15parts by weight per part by weight of herbicide. Which ratio with regardto the optimum effect on the specific cultivated plant is most suitableis determined from case to case, i.e. depending on the type of herbicideused.

As already mentioned, various methods and techniques are suitable forthe application of the novel antidotes of the formulae I-III forprotecting cultivated plants against agricultural chemicals, or forstimulating plant growth.

(1) Seed dressing

(a) Dressing of the seed with an active substance formulated as awettable powder by shaking in a vessel until there exists a uniformdistribution over the surface of the seeds (dry dressing). The amount ofactive substance of the formula I used for this purpose is about 10 to500 g (40 g to 2 kg of wettable powder) per 100 kg of seed.

(1) Dressing of the seed with an emulsion concentrate of the activesubstance of the formula I using method (a) (wet dressing).

(c) Dressing by immersion of the seed in a liquor containing 50-3200 ppmof active substance of the formula I for 1-72 hours and, optionally,subsequent drying of the seed (immersion dressing).

The dressing of the seed or the treatment of the germinated seedlingsare naturally the preferred methods of application because the treatmentwith the active substance is directed completely at the target crop.There is used as a rule 10 g to 500 g, preferably 50 to 250 g, of activesubstance per 100 kg of seed, with it being possible, depending on themethod used, which enables also the addition of other active substancesor micronutrients to be made, to deviate either upwards or downwardsfrom the given limiting concentrations (repeat dressings).

(2) Application as a tank mixture

A liquid preparation of a mixture of antidote and herbicide (reciprocalquantitative ratio between 10:1 and 1:10) is used, the applied amount ofherbicide being 0.1 to 10 kg per hectare. A tank mixture of this kind ispreferably applied before or immediately after sowing, or it is workedinto the unsown soil to a depth of 5-10 cm.

(3) Application into the seed furrow

The antidote is introduced, as an emulsion concentrate, wettable powderor granulate, into the open sown seed furrow and, after the covering ofthe seed furrow in the normal manner, the herbicide is applied using thepre-emergence process.

Essentially, the antidote can therefore be applied before, togetherwith, or after the pesticide, and its application to the seeds or to thefield can be effected either before or after sowing, or in certain casesalso after germination of the seed. The invention relates in particularalso to compositions which contain, besides the antidote of the formulaI, at least one agrochemical active substance, e.g. a herbicide from thechloroacetanilide class or from the thiolcarbamate class. Thesecompositions contain in addition also carrier substances and/ordistributing agents.

(4) Controlled release of active substance

The active substance in solution is absorbed onto mineral granulatecarriers or onto polymerized granulates (urea/formaldehyde), and thematerial is allowed to dry. It is possible if desired to apply a coating(coated granules), which enables the active substance to be released incontrolled amounts over a specific period of time.

It is naturally possible to use also all other known methods of applyingactive substances. Examples in this respect are given further on in thetext.

The process according to the invention for promoting plant growth or forprotecting cultivated plants can be applied in particular to rice and tocultivated millet of the sorghum variety, also to maize, wheat, barley,oats, soya bean, cotton and sugar beet. It is however not limited to thepromotion and protection of annual plants, but is also very suitable forgrowth stimulation of perennial plants (fruit trees, ornamental shrubs,and so forth), where it is desired to promote root formation or theformation of side shoots, or to achieve improved fruit setting orimproved influorescence.

The compounds of the formula I are produced by processes known per se(Organic Reactions 1953, Vol. 7, pages 343 and 373; Journal f. prakt.Chemie 66, page 353; Lfebig. Ann. 250, 165.), namely by etherificationor acylation of an oxime of the formula V ##STR11## or of its oximesalt, with a halide of the formula Halg--Q, wherein Ar, X and Q have themeanings given for the formula I, and "Halg" denotes halogen, preferablythiorine or bromine.

The condensation of substituted α-oximino compounds is effected in thecase of etherification advantageously with the compounds in the form oftheir salts, particularly in the form of their alkali metal salts orammonium salts, as is shown in the following by selected examples:##STR12##

Acylation is effected advantageously with the free oximes of the formulaV, as is shown by the following diagrams: ##STR13## (In the abovediagrams, "Halg" denotes halogen, especially Cl or Br)

Suitable as solvents for obtaining the compounds of the formula I areessentially all representatives which behave inertly under theconditions of the reaction. For example, hydrocarbons, particularlyhowever polar solvents, such as acetonitrile, dioxane, cellosolve orDMT, but also ketones, such as methyl ethyl ketone, acetone, etc.Solvents containing hydroxyl groups are excluded.

The temperatures are in the range of -10° C. to about 150° C.,preferably between 20° and 120° C.

As agents splitting off hydrogen halide, it is possible to use basessuch as tert. amines (triethylamine, triethylenediamine, piperidine,etc.). Also a suspension of sodium carbonate in the anhydrous reactionmedium suffices in some cases.

Oximes are present in two stereoisomeric forms, the syn-form andanti-form. Also the compounds of the formula I mentioned under (a) to(e) can be present in either of these forms in the pure state or asmixtures of both. By `compounds of the formula I` are accordingly meant,within the scope of the present specification, both stereoisomeric formson their own, or as mixtures with each other in any reciprocalquantitative ratio.

The following Examples illustrate the production of the novel oximes ofthe formula I.

EXAMPLE 1

17 g (0.1 mol) of phenylglyoxylonitrile-2-oxime sodium salt is suspendedin 170 ml of acetonitrile in a 350 ml sulphonating flask. There is thenadded 23.8 g (0.1 mol) of chloroaceto-3,4-dichloroanilide, whereupon aslight reaction heating can be detected. The suspension is refluxed for3 hours, with the suspension changing in appearance. After cooling toroom temperature, the formed sodium chloride is filtered off; theresidue is subsequently washed with acetonitrile, and the combinedfiltrates are then concentrated in vacuo to leave as residue 32.3 g ofcrude product. Recrystallisation from alcohol/water yields 20.4 g offinal product of the formula ##STR14## m.p. 143°-144° C.

From the salt of 2,4-dimethylphenylhydroxamic acid chloride and allylchloride, there is correspondingly obtained as an oily substance theproduct of the formula ##STR15##

In a similar manner is obtained from 2-thienylacetonitrileoxime sodiumsalt and chloroacetonitrile the compound ##STR16## as oily substance.

EXAMPLE 2

33.6 g (0.2 mol) of phenylglyoxylonitrile-oxime sodium salt and 25 g(0.22 mol) of chloroacetic acid methyl ester in 200 ml of acetonitrileare held for 3 hours at 60°-70° C. with thorough stirring, in which timethe suspension becomes greatly refined. After a further few hours,filtration is performed; the residue is subsequently washed withacetonitrile, and the combined filtrates are concentrated in vacuo toleave an oily residue, which becomes solid after about 24 hours, m.p.68°-70° C.; Recrystallised from isopropanol: m.p. 71°-72° C. ##STR17##

In a similar manner is obtained, by condensation of4-chlorophenylglyoxylonitrile-oxime sodium salt with α-chloropropionicacid ethyl ester, the compound of the formula ##STR18## in 99.3% yieldin the form of oil.

If there is used, instead of the α-chloropropionic acid ester, thechloroacetic acid isopropyl ester, there is obtained the compound of theformula ##STR19## and with use of the unsubstitutedphenylglyoxylonitrile oxime (as Na salt) there is obtained the compoundof the formula ##STR20##

EXAMPLE 3 Production of ##STR21## α-Cyanobenzylidene-amino-oxacetamide

845 g (5 mols) of benz-acetonitrileoxime as Na salt is suspended in 2.5liters of acetonitrile, and there is slowly added in the presence ofcatalytic amounts of KJ, with stirring, 468 g (5 mols) ofchloroacetamide. The reaction mixture is refluxed for 12 hours; it isthen cooled and subsequently allowed to flow into about 12 liters ofwater. While the salts present are dissolving, the final productprecipitates in crystalline form: 882 g (=86.8% of theory), m.p.128°-129° C. (from ethanol).

There is correspondingly obtained, from the sodium salt of3-furanylnitromethane-oxime and methanesulphonyl chloride, the compoundof the formula ##STR22## in the form of viscous oil.

EXAMPLE 4

8.0 g (0.037 mol) of the sodium salt of α-oximino-1-naphthylacetonitrileand 5.5 g (0.045 mol) of propargyl bromide in 50 ml of acetonitrile areheated for 4 hours at about 80° C. The suspension is afterwardsconcentrated in vacuo, and the residue is extracted with methylenechloride. The solution is concentrated by evaporation to leave thecompound of the formula ##STR23## as oil.

Analysis for C₁₅ H₁₀ N₂ O. Calculated: C 76.9%, H 4.3%, N 11.96%. Found:C 76.4%, H 4.4%, N 11.8%.

If there is used as reactant, instead of propargyl bromide,chloroacetonitrile, there is obtained the compound of the formula##STR24##

EXAMPLE 5

0.1 mol of the sodium salt of α-oximino-2-thienylacetonitrile with 0.12mol of chloroacetamide is suspended in 150 ml of acetonitrile. Thesuspension is heated for 3 hours at 50°-60° C., with NaCl precipitating;this is filtered off and washed with acetonitrile. The filtrates areconcentrated in vacuo to yield the compound of the formula ##STR25## asa light-yellow oily substance.

The temperatures are given in degrees Centigrade in the followingTables.

The following compounds can be produced by the methods described above:

    __________________________________________________________________________     ##STR26##                                                                     Comp.                                                                        No. R.sub.1                                                                             R.sub.2                                                                           Q                                                               __________________________________________________________________________    1.1 H     H   CH.sub.2CONH.sub.2  m.p. 128-129°                        1.2 4-Cl  H   CH.sub.2CONH.sub.2  m.p. 126-128°                        1.3 H     H   CH.sub.2COOCH.sub.3 m.p. 71-72°                          1.4 H     H   CH.sub.2COOC.sub.2 H.sub.5                                                                        m.p. 54-56°                          1.5 H     H   CH.sub.2COO(i-C.sub.3 H.sub.7)                                                                    m.p. 49-50°                          1.6 4-CH.sub.3                                                                          H   CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.7 4-Cl  H   CH.sub.2COO(i-C.sub.3 H.sub.7)                                                                    m.p. 93-94°                          1.8 4-Cl  2-Cl                                                                              CH.sub.2COOCH.sub.3 oil                                         1.9 4-Cl  2-Cl                                                                              CH.sub.2COOC.sub.2 H.sub.5                                                                        oil                                         1.10                                                                              4-Cl  3-Cl                                                                              CH.sub.2COOCH.sub.3 oil                                         1.11                                                                              4-Cl  3-Cl                                                                              CH.sub.2COOC.sub.2 H.sub.5                                                                        oil                                         1.12                                                                              4-Cl  H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    oil                                         1.13                                                                              4-CH.sub.3 O                                                                        H   CH.sub.2COOC.sub.2 H.sub.5                                                                        m.p. 78-81°                          1.14                                                                              H     H   CH.sub.2CCH         oil                                         1.15                                                                              H     2-Cl                                                                              C.sub.2 H.sub.5     oil                                         1.16                                                                              4-CH.sub.3                                                                          H   nC.sub.3 H.sub.7    oil                                         1.17                                                                              4-CH.sub.3 O                                                                        H   CH.sub.3            m.p. 75-77°                          1.18                                                                              4-CH.sub.3 O                                                                        H   C.sub.2 H.sub.5     oil                                         1.19                                                                              4-Br  H   CH.sub.2CCH         m.p. 90-92°                            1.20                                                                            H     H                                                                                  ##STR27##          b.p. 118-120°/0.8 Torr                 1.21                                                                            4-Cl  H   CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                             oil                                         1.22                                                                              4-Cl  H   CH.sub.2CCH         semisolid                                   1.23                                                                              4-Cl  H   CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.24                                                                              4-CH.sub.3                                                                          H   C.sub.2 H.sub.5     oil                                         1.25                                                                              4-Cl  2-Cl                                                                              CH(CH.sub.3)CCH     oil                                         1.26                                                                              4-Br  H    CH.sub.3           m.p. 60-62°                          1.27                                                                              3-CF.sub.3                                                                          H   CH.sub.2COOC.sub.2 H.sub.5                                      1.28                                                                              3-CF.sub.3                                                                          H   CH.sub.2HCCH.sub.2                                              1.29                                                                              H     H   nC.sub.4 H.sub.9                                                1.30                                                                              H     H   CH.sub.2COO(isoC.sub.4 H.sub.9)                                 1.31                                                                              3-CF.sub.3                                                                          H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                  1.32                                                                              4-NO.sub.2                                                                          H   CH.sub.2COOCH.sub.3                                             1.33                                                                              4-NO.sub.2                                                                          H   CH.sub.2CONH.sub.2                                                1.34                                                                            H     H                                                                                  ##STR28##          m.p. 143-144°                          1.35                                                                            H     H   SO.sub.2 N(CH.sub.3).sub.2                                                                        m.p. 88-89°                          1.36                                                                              4-Br  H   CH.sub.2CN          m.p. 77-79°                          1.37                                                                              4-CH.sub.3 O                                                                        H   C.sub.2 H.sub.5     solid                                       1.38                                                                              H     H   CH.sub.3            m.p. 129-131°                        1.39                                                                              H     H   C.sub.2 H.sub.5     oil                                         1.40                                                                              H     H   C.sub.3 H.sub.7 (iso)                                                                             oil                                         1.41                                                                              H     H   CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.42                                                                              H     H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    m.p. 36-37°                          1.43                                                                              H     H   CH(C.sub.2 H.sub. 5)COOC.sub.2 H.sub.5                                                            solid                                       1.44                                                                              H     H   CH.sub.2CH.sub.2CN  m.p. 123-126°                        1.45                                                                              H     H   CH.sub.2CH.sub.2CH.sub.2CN                                                                        oil                                         1.46                                                                              H     H   COCH.sub.3          m.p. 68-70°                          1.47                                                                              3-CF.sub.3                                                                          H   CH.sub.2COOCH.sub.3 m.p. 107-109°                        1.48                                                                              2-CH.sub.3                                                                          H   CH.sub.2CN                                                      1.49                                                                              2-F   H   CH.sub.2CN                                                      1.50                                                                              2-F   H   CH.sub.2CONH.sub.2  oil                                         1.51                                                                              2-CH.sub.3                                                                          H   CH(CH.sub.3)COOCH.sub.3                                           1.52                                                                            4-Cl  H                                                                                  ##STR29##          m.p. 158-160°                          1.53                                                                            H     H                                                                                  ##STR30##          m.p. 97-99°                            1.54                                                                            H     H   (CH.sub.2).sub.7CH.sub.3                                                                          m.p. 131-133°                        1.55                                                                              4-nC.sub.4 H.sub.9 O                                                                H   CH.sub.2CN                                                      1.56                                                                              4-isoC.sub.3 H.sub.7 O                                                              H   CH.sub.2CONH.sub.2                                              1.57                                                                              2-CH.sub.3                                                                          H   CH.sub.2CONH.sub.2  oil                                         1.58                                                                              3-NO.sub.2                                                                          H   CH.sub. 2CONH.sub.2                                             1.59                                                                              3-NO.sub.2                                                                          H   SO.sub.2CH.sub.3    m.p. 133-135°                        1.60                                                                              H     H   CH.sub.2COCH.sub.3  m.p. 67-68°                          1.61                                                                              H     H   CH(CH.sub.3)CONH.sub.2                                                                            m.p. 144-146°                        1.62                                                                              H     H   SO.sub.2CH.sub.3    m.p. 121-122°                        1.63                                                                              H     H   CH.sub.2COOC.sub.4 H.sub.9 (tert.)                                                                m.p. 76-77°                          1.64                                                                              H     H   CH(nC.sub.10 H.sub.21)COOC.sub.2 H.sub.5                                                          m.p. 53-54°                          1.65                                                                              H     H   C(CH.sub.3).sub.2COOC.sub.2 H.sub.5                                                               oil                                         1.66                                                                              H     H   CH(CH.sub.3)COOC.sub.3 H.sub.7 (iso)                                                              oil                                         1.67                                                                              H     H   (CH.sub.2).sub.17CH.sub.3                                                                         solid                                       1.68                                                                              H     H   CH(CH.sub.3)CCH     oil                                         1.69                                                                              H     H   CH(CH.sub.3)CON(C.sub.2 H.sub.5).sub.2                                                            oil                                         1.70                                                                              H     H   CH.sub.2CONHCH.sub.3                                            1.71                                                                              H     H   CH.sub.2CON(CH.sub.3).sub.2                                     1.72                                                                              H     H   CH.sub.2CONHCH.sub.2CHCH.sub.2                                  1.73                                                                              H     H   CH.sub.2CONHC CH                                                1.74                                                                              H     H   CH.sub.2CON(CH.sub.3)CH.sub.2CHCH.sub.2                         1.75                                                                              H     H   CH.sub.2CON(CH.sub.3)C.sub.2 H.sub.5                            1.76                                                                              H     H   CH(CH.sub.3)CONHCH.sub.3                                        1.77                                                                              H     H   CH(CH.sub.3)CON(CH.sub.3).sub.2                                 1.78                                                                              H     H   CH.sub.2CON(allyl).sub.2                                                                          solid                                       1.79                                                                              H     H   C.sub.6 H.sub.3 (NO.sub.2).sub.2 (2,4)                                                            m.p. 178-179°                        1.80                                                                              H     H   CH.sub.2C.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            m.p. 91-93°                          1.81                                                                              H     H   CH.sub.2COOCH.sub.2C.sub.6 H.sub.5                                                                m.p. 61-62°                          1.82                                                                              H     H   CH.sub.2COOC.sub.6 H.sub.4 NO.sub.2 (4)                                                           solid                                       1.83                                                                              H     H   CH.sub.2CONHC.sub.6 H.sub.3 Cl.sub.2 (3,5)                                                        m.p. 149-150°                        1.84                                                                              H     H   CH.sub.2CONHC.sub.6 H.sub.4 F(4)                                                                  m.p. 136-137°                        1.85                                                                              H     H   COC.sub.2 H.sub.5   m.p. 53-55°                          1.86                                                                              H     H   CH(CH.sub.3)CN      m.p. 60-62°                          1.87                                                                              H     H   CH.sub.2CHCHCH.sub.3                                                                              oil                                         1.88                                                                              4-CH.sub.3                                                                          H   CH.sub.2CN          m.p. 82-84°                          1.89                                                                              4-CH.sub.3                                                                          H   CH.sub.3            m.p. 44-46°                          1.90                                                                              4-CH.sub.3                                                                          H   CH.sub.2COOCH.sub.3 solid                                       1.91                                                                              4-CH.sub.3                                                                          H   CH.sub.2COOC.sub.2 H.sub.5                                                                        solid                                       1.92                                                                              4-CH.sub.3                                                                          H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    oil                                         1.93                                                                              4-CH.sub.3                                                                          H   CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                             oil                                         1.94                                                                              4-CH.sub.3                                                                          H   CH.sub.2CONHC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                        m.p. 162-164°                        1.95                                                                              4-CH.sub.3                                                                          H   CH(CH.sub.3)COOC.sub.3 H.sub.7 (iso)                                                              oil                                         1.96                                                                              4-CH.sub.3                                                                          H   CH.sub.2CCH         solid                                       1.97                                                                              4-CH.sub.3                                                                          H   CH.sub.2 CHCHCH.sub.3                                                                             oil                                         1.98                                                                              4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2CN          m.p. 40°                             1.99                                                                              4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.3            oil                                         1.100                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        C.sub.2 H.sub.5     oil                                         1.101                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        C.sub.3 H.sub.7 (n) oil                                         1.102                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2COOCH.sub.3 m.p. ca. 60°                         1.103                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2COOC.sub.2 H.sub.5                                                                        m.p. ca. 50°                         1.104                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.105                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    oil                                         1.106                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2CCH         m.p. 75-81°                          1.107                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2CONHC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                        m.p. 110°                            1.108                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2CONHCH.sub.3                                                                              oil                                         1.109                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2CON(CH.sub.3)CH.sub.2CHCH.sub.2                                                           oil                                         1.110                                                                             4-CH.sub.3                                                                          3-CH.sub.3                                                                        CH.sub.2CONH.sub.2  oil                                         1.111                                                                             4-OCH.sub.3                                                                         H   CH.sub.2CN          m.p. 91-93°                          1.112                                                                             4-OCH.sub.3                                                                         H   C.sub.3 H.sub.7 (n) oil                                         1.113                                                                             4-OCH.sub.3                                                                         H   CH.sub.2COOCH.sub.3 m.p. 122-125°                        1.114                                                                             4-OCH.sub.3                                                                         H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    m.p. 50-53°                          1.115                                                                             4-OCH.sub.3                                                                         H   CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.116                                                                             4-OCH.sub.3                                                                         H   CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                             oil                                         1.117                                                                             4-OCH.sub.3                                                                         H   CH(CH.sub.3)CCH     solid                                       1.118                                                                             4-OCH.sub.3                                                                         H   CH.sub.2COOC.sub.3 H.sub.7 (iso)                                                                  solid                                       1.119                                                                             4-OCH.sub.3                                                                         H   CH(CH.sub.3)COOC.sub.3 H.sub.7 (iso)                                                              oil                                         1.120                                                                             4-OCH.sub.3                                                                         H   (CH.sub.2).sub.7CH.sub.3                                                                          oil                                         1.121                                                                             4-OCH.sub.3                                                                         H   CH.sub.2CONH.sub.2  m.p. 123-126°                        1.122                                                                             4-OCH.sub.3                                                                         H   CH.sub.2CCH         solid                                       1.123                                                                             4-OCH.sub.3                                                                         H   CH.sub.2CHCH.sub.2  m.p. ca. 40°                         1.124                                                                             4-OCH.sub.3                                                                         H   COC.sub.6 H.sub.5   m.p. 128-130°                        1.125                                                                             4-OCH.sub.3                                                                         H   CH.sub.2CHCHCH.sub.3                                                                              solid                                       1.126                                                                             4-Cl  H   CH.sub.2CN          m.p. 69-71°                          1.127                                                                             4-Cl  H   CH.sub.3            m.p. 70-71°                          1.128                                                                             4-Cl  H   C.sub.2 H.sub.5     m.p. 39-40°                          1.129                                                                             4-Cl  H   C.sub.3 H.sub.7 (n) oil                                         1.130                                                                             4-Cl  H   CH.sub.2COOCH.sub.3 m.p. 81-82°                          1.131                                                                             4-Cl  H   CH.sub.2COOC.sub.2 H.sub.5                                                                        m.p. 79-80°                          1.132                                                                             4-Cl  H   CH(CH.sub.3)COOC.sub.3 H.sub.7 (iso)                                                              oil                                         1.133                                                                             4-Cl  H   (CH.sub.2).sub.7CH.sub. 3                                                                         oil                                         1.134                                                                             4-Cl  H   CH.sub.2CHCH.sub.2  solid                                       1.135                                                                             4-Cl  H   CH.sub.2CONHC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                        m.p. 165-166°                        1.136                                                                             4-Cl  H   CH.sub.2CONHC.sub.6 H.sub.4 Br(4)                                                                 m.p. 199-201°                        1.137                                                                             4-Cl  H   CH.sub.2CONHC.sub.6 H.sub.4 CF.sub.3 (3)                                                          m.p. 187-190°                        1.138                                                                             4-Cl  H   CH.sub.2CONHC.sub.6 H.sub.4 Cl(4)                                                                 m.p. 204-205°                        1.139                                                                             2-Cl  H   CH.sub.2CN          m.p. 51-53°                          1.140                                                                             2-Cl  H   CH.sub.3            oil                                         1.141                                                                             2-Cl  H   C.sub.3 H.sub.7 (n) oil                                         1.142                                                                             4-Cl  2-Cl                                                                              CH.sub.2CN          m.p. 126-128°                        1.143                                                                             4-Cl  2-Cl                                                                              CH.sub.3            m.p. 95-96°                          1.144                                                                             4-Cl  2-Cl                                                                              C.sub.2 H.sub.5     solid                                       1.145                                                                             4-Cl  2-Cl                                                                              CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.146                                                                             4-Cl  2-Cl                                                                              CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    oil                                         1.147                                                                             4-Cl  2-Cl                                                                              CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                             oil                                         1.148                                                                             4-Cl  2-Cl                                                                              CH.sub.2CCH         solid                                       1.149                                                                             4-Cl  2-Cl                                                                              CH.sub.2CHCHCH.sub.3                                                                              oil                                         1.150                                                                             4-Cl  3-Cl                                                                              CH.sub.3            m.p. 84-85°                          1.151                                                                             4-Cl  3-Cl                                                                              C.sub.2 H.sub.5     solid                                       1.152                                                                             4-Cl  3-Cl                                                                              C.sub.3 H.sub.7 (n) oil                                         1.153                                                                             4-Cl  3-Cl                                                                              C.sub.4 H.sub.9 (tert.)                                                                           solid                                       1.154                                                                             4-Cl  3-Cl                                                                              CH(CH.sub.3)COOCH.sub.3                                                                           solid                                       1.155                                                                             4-Cl  3-Cl                                                                              CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    oil                                         1.156                                                                             4-Cl  3-Cl                                                                              CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                             oil                                         1.157                                                                             4-Cl  3-Cl                                                                              CH.sub.2CN          m.p. 90-93°                          1.158                                                                             4-Cl  3-Cl                                                                              CH.sub.2CCH         solid                                       1.159                                                                             4-Br  H   C.sub.2 H.sub.5     solid                                       1.160                                                                             4-Br  H   C.sub.3 H.sub.7 (n) solid                                       1.161                                                                             4-Br  H   CH.sub.2COOCH.sub.3 solid                                       1.162                                                                             4-Br  H   CH.sub.2COOC.sub.2 H.sub.5                                                                        m.p. ca. 40°                         1.163                                                                             4-Br  H   CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.164                                                                             4-Br  H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                    oil                                         1.165                                                                             4-Br  H   CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                             oil                                         1.166                                                                             4-Br  H   CH.sub.2CHCH.sub.2  m.p. 90-92°                          1.167                                                                             4-Br  H   CH.sub.2CONH.sub.2  m.p. 147- 149°                       1.168                                                                             4-Br  H   CH(CH.sub.3)CCH     m.p. ca. 50°                         1.169                                                                             4-Br  H   CH.sub.2COOC.sub.3 H.sub.7 (iso)                                                                  solid                                       1.170                                                                             4-Br  H   CH(CH.sub.3)COOC.sub.3 H.sub.7 (iso)                                                              oil                                         1.171                                                                             4-Br  H   CH.sub.2CHCHCH.sub.3                                                                              oil                                         1.172                                                                             4-Br  H   CH.sub.2CONHC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                        m.p. 152-155°                        __________________________________________________________________________

There are obtained analogously also the following compounds of theformula

    __________________________________________________________________________     ##STR31##                                                                    Comp.                                                                         No. R.sub.1                                                                             R.sub.2                                                                           Q                                                               __________________________________________________________________________    1.173                                                                             H     H   CH.sub.2CN          oil                                         1.174                                                                             H     H   CH.sub.2CONH.sub.2  oil                                         1.175                                                                             4-Cl  H   CH.sub.2CONH.sub.2  oil                                         1.176                                                                             H     H   CH.sub.2COOCH.sub.3                                             1.177                                                                             H     H   CH.sub.2COOC.sub.2 H.sub.5                                      1.178                                                                             H     H   CH.sub.2COO(i-C.sub.3 H.sub.7)                                  1.179                                                                             4-CH.sub.3                                                                          H   CH(CH.sub.3)COOCH.sub.3                                         1.180                                                                             4-Cl  H   CH.sub.2COO(i-C.sub.3 H.sub.7)                                  1.181                                                                             4-Cl  2-Cl                                                                              CH.sub.2COOCH.sub.3                                             1.182                                                                             4-Cl  2-Cl                                                                              CH.sub.2COOC.sub.2 H.sub.5                                      1.183                                                                             4-Cl  3-Cl                                                                              CH.sub.2COOCH.sub.3                                             1.184                                                                             4-Cl  3-Cl                                                                              CH.sub.2COOC.sub.2 H.sub.5                                      1.185                                                                             4-Cl  H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                  1.186                                                                             4-CH.sub.3 O                                                                        H   CH.sub.2COOC.sub.2 H.sub.5                                      1.187                                                                             H     H   CH.sub.2C CH        oil                                         1.188                                                                             H     H   CH.sub.2CON(CH.sub.3).sub.2                                     1.189                                                                             4-CH.sub.3                                                                          H   nC.sub.3 H.sub.7                                                1.190                                                                             4-CH.sub.3 O                                                                        H   CH.sub.3                                                        1.191                                                                             H     H   CH.sub.2CONHCCH     oil                                         1.192                                                                             4-Br  H   CH.sub.2CCH                                                     1.193                                                                             H     H   CH.sub.2CON(CH.sub.3)C.sub.2 H.sub.5                                                              oil                                         1.194                                                                             H     H   CH.sub.2CON(CH.sub.3)CH.sub.2CHCH.sub.2                                                           oil                                         1.195                                                                             4-Cl  H   CH.sub.2CCH                                                     1.196                                                                             4-Cl  2-Cl                                                                              CH(CH.sub.3)CCH                                                 1.197                                                                             3-CF.sub.3                                                                          H   CH.sub.2COOC.sub.2 H.sub.5                                      1.198                                                                             3-CF.sub.3                                                                          H   CH.sub.2HCCH.sub.2                                              1.199                                                                             H     H   CH.sub.2CONHCH.sub.2CHCH.sub.2                                                                    oil                                         1.200                                                                             3-CF.sub.3                                                                          H   CH(CH.sub.3)COOC.sub.2 H.sub.5                                  1.201                                                                             4-NO.sub.2                                                                          H   CH.sub.2CONH.sub.2  oil                                           1.202                                                                           H     H                                                                                  ##STR32##          oil                                           1.203                                                                           4-Cl  H   CH(CH.sub.3)COOCH.sub.3                                                                           oil                                         1.204                                                                             4-NO.sub.2                                                                          H   CH.sub.2 COOCH.sub.3                                                                              solid                                       1.205                                                                             H     H   COCH.sub.2NH.sub.2                                              1.206                                                                             3-CF.sub.3                                                                          5-CF.sub.3                                                                        CH.sub.2COOCH.sub.3                                             1.207                                                                             2-CH.sub.3                                                                          H   CH.sub.2CN          oil                                         1.208                                                                             2-F   H   CH.sub.2CN          oil                                         1.209                                                                             2-F   H   CH.sub.2CONH.sub.2  oil                                         1.210                                                                             2-CH.sub.3                                                                          H   CH(CH.sub.3)COOCH.sub.3                                         1.211                                                                             4-nC.sub.4 H.sub.9 O                                                                H   CH.sub.2CN          oil                                         1.212                                                                             4-isoC.sub.3 H.sub.7 O                                                              H   CH.sub.2CONH.sub.2  oil                                         1.213                                                                             2-CH.sub.3                                                                          H   CH.sub.2CONH.sub.2  oil                                         1.214                                                                             3-NO.sub.2                                                                          H   CH.sub.2CONH.sub.2  oil                                         1.215                                                                             3-NO.sub.2                                                                          H   SO.sub.2CH.sub.3                                                1.216                                                                             2-CH.sub.3                                                                          4-CH.sub.3                                                                        CH.sub.2CHCH.sub.2                                              __________________________________________________________________________

There are obtained analogously also the following compounds of theformula

    __________________________________________________________________________     ##STR33##                                                                    Comp.                                                                         No. R.sub.1                                                                           R.sub.2                                                                           X          Q                                                      __________________________________________________________________________    1.217                                                                             H   H   COCH.sub.3 CH.sub.2CN        oil                                  1.218                                                                             H   H   COCH.sub.3 CH.sub.2CONH.sub.2                                                                              oil                                  1.219                                                                             H   H   COCH.sub.3 CH.sub.2 COOCH.sub.3                                                                            oil                                  1.220                                                                             H   H   COCH.sub.3 CH(CH.sub.3)COOCH.sub.3                                1.221                                                                             4-Cl                                                                              H   COCH.sub.3 CH.sub.2CN                                             1.222                                                                             4-CH.sub.3                                                                        2-CH.sub.3                                                                        COCH.sub.3 CH.sub.2CN                                             1.223                                                                             3-CF.sub.3                                                                        H   COCH.sub.3 CH.sub.2CONH.sub.2                                     1.224                                                                             4-Cl                                                                              2-NO.sub.2                                                                        COCH.sub.3 CH.sub.2COOCH.sub.3                                    1.225                                                                             H   H   COCH.sub.3 C.sub.2 H.sub.5                                        1.226                                                                             H   H   COCH.sub.3 CH.sub.2CHCH.sub.2                                     1.227                                                                             H   H   COOC.sub.2 H.sub.5                                                                       CH.sub.2CN        oil                                  1.228                                                                             H   H   COOC.sub.2 H.sub.5                                                                       CH.sub.2 CCH                                           1.229                                                                             H   H   COOC.sub.2 H.sub.5                                                                       CH.sub.2CONH.sub.2                                     1.230                                                                             H   H   COOC.sub.2 H.sub.5                                                                       CH.sub.2CON(CH.sub.3).sub.2                            1.231                                                                             H   H   COOC.sub.2 H.sub.5                                                                       CH.sub.3          oil                                  1.232                                                                             H   H   NO.sub.2   CH.sub.2CN        oil                                  1.233                                                                             H   H   NO.sub.2   CH.sub.2CONH.sub.2                                                                              oil                                  1.234                                                                             H   H   NO.sub.2   CH.sub.2CONHC.sub.3 H.sub.7 (n)                          1.235                                                                           H   H   NO.sub.2                                                                                  ##STR34##                                               1.236                                                                           H   H   NO.sub.2   CH.sub.2SO.sub.2 N(CH.sub.3).sub.2                     1.237                                                                             H   H   NO.sub.2   CH.sub.2COOC.sub.2 H.sub.5                             1.238                                                                             H   H   NO.sub.2   CH(CH.sub.3)COOCH.sub.3                                1.239                                                                             H   H   CONHCH.sub.3                                                                             CH.sub.2CH        oil                                  1.240                                                                             H   H   CONHCH.sub.3                                                                             CH.sub.2CONHCH.sub.3                                   1.241                                                                             H   H   CONHCH.sub.3                                                                             CH.sub.3                                               1.242                                                                             H   H   CONHCH.sub.3                                                                             CH.sub.2C CH      oil                                  1.243                                                                             H   H   CH.sub.3   CH.sub.2CN                                             1.244                                                                             H   H   CH.sub.3   CH.sub.2CONH.sub.2                                                                              oil                                  1.245                                                                             H   H   CH.sub.3   CH.sub.2COOCH.sub.3                                    1.246                                                                             H   H   CH.sub.3   (CH.sub.3)COO(iC.sub.3 H.sub.7)                        1.247                                                                             H   H   CH.sub.3   CH.sub.2CONHCH.sub.3                                   1.248                                                                             H   H   CH.sub.3   CH.sub.2CONHCH.sub.2 CCH                               1.249                                                                             H   H   CH.sub.3   CH.sub.2CONHCH.sub.2CHCH.sub.2                         1.250                                                                             H   H   CH.sub.3   CH.sub.2CHCH.sub.2                                     1.251                                                                             2-F H   CH.sub.3   CH.sub.2COOC.sub.2 H.sub.5                             1.252                                                                             2-CH.sub.3                                                                        5-CH.sub.3                                                                        CH.sub.3   CH.sub.2CH.sub.2OCH.sub.3                              1.253                                                                             H   H   COOCH.sub.3                                                                              CH.sub.2CN                                             1.254                                                                             3-NO.sub.2                                                                        H   COOCH.sub.3                                                                              CH.sub.2COOCH.sub.3                                    1.255                                                                             H   H   COOCH.sub.3                                                                              CH.sub.2CONH.sub.2                                     1.256                                                                             H   H   COOCH.sub.3                                                                              CH.sub.3                                               1.257                                                                             H   H   COOCH.sub. 3                                                                             nC.sub.5 H.sub.11                                      1.258                                                                             H   H   COOCH.sub.3                                                                              CH.sub.2CON(allyl).sub.2                               1.259                                                                             H   H   COOCH.sub.3                                                                              CH(CH.sub.3)COOCH.sub.3                                1.260                                                                             H   2-Cl                                                                              COOCH.sub.3                                                                              CH.sub.2CN                                             1.261                                                                             4-Cl                                                                              3-Cl                                                                              COOCH.sub.3                                                                              CH.sub.2COOCH.sub.3                                    1.262                                                                             2-Cl                                                                              2-NO.sub.2                                                                        COOCH.sub.3                                                                              CH.sub.2CN                                             1.263                                                                             2-Cl                                                                              2-NO.sub.2                                                                        COOCH.sub.3                                                                              CH.sub.2CN                                             1.264                                                                             H   H   H          CH.sub.2CN                                             1.265                                                                             H   H   H          CH.sub.2CONH.sub.2                                     1.266                                                                             H   H   COCH.sub.2 CCH                                                                           CH.sub.2CCH                                            1.267                                                                             H   H   COCH.sub.2 CCH                                                                           CH.sub.2CN                                             1.268                                                                             H   H   CO CH.sub.2 CCH                                                                          CH.sub.2CONH.sub.2                                     1.269                                                                             H   H   COCH.sub.2 CCH                                                                           CH.sub.2CONHCH.sub.3                                   1.270                                                                             H   H   COCH.sub.2 CCH                                                                           CH.sub.2CHCH.sub. 2                                    1.271                                                                             H   H   COCH.sub.2 CCH                                                                           CH.sub.3                                               1.272                                                                             H   H   CONH.sub.2 CH.sub.2CN                                             1.273                                                                             H   H   CONH.sub.2 CH.sub.2CONH.sub.2                                     1.274                                                                             H   H   Br         CH.sub.2CN                                             1.275                                                                             H   H   Br         CH.sub.2CONH.sub.2                                     1.276                                                                             H   H   Cl         CH.sub.2CH.sub.2CN                                     1.277                                                                             H   H   COCH.sub.3 CH.sub.2CH.sub.2CN                                     1.278                                                                             H   H   COOCH.sub.3                                                                              CH.sub.2CH.sub.2CN                                     1.279                                                                             H   H   CONH.sub.2 CH.sub.2CH.sub.2CN                                     __________________________________________________________________________

Similarly important products are the compounds derived fromnaphthylglyoxylonitrile and from analogous derivatives; for examplecompounds of the formula

    __________________________________________________________________________     ##STR35##                                                                    Comp.                                                                         No. X      Q                                                                  __________________________________________________________________________    2.1 CN     CH.sub.2CN         m.p. 81-82°                              2.2 CN     CH.sub.2CONH.sub.2 semisolid                                       2.3 CN     CH(CH.sub.3)CCH    oil                                             2.4 CN     CH.sub.2CCH        oil                                             2.5 CN     CH.sub.2CHCH.sub.2 oil                                             2.6 CN     CH.sub.3           oil                                             2.7 CN     C.sub.2 H.sub.5    oil                                             2.8 CN     n-C.sub.3 H.sub.7  oil                                             2.9 CN     CH.sub.2COOCH.sub.3                                                                              semisolid                                       2.10                                                                              CN     CH.sub.2COOC.sub.2 H.sub.5                                                                       oil                                             2.11                                                                              CN     CH(CH.sub.3)COOCH.sub.3                                                                          oil                                             2.12                                                                              CN     CH(CH.sub.3)COOC.sub.2 H.sub.5                                                                   oil                                             2.13                                                                              CN     CH(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                              2.14                                                                              CN     COC.sub.6 H.sub.5  m.p. 115-118°                              2.15                                                                            CN                                                                                    ##STR36##                                                           2.16                                                                            CN     SO.sub.2CH.sub.3                                                   2.17                                                                              CN     CH(CH.sub.3)COO(isoC.sub.3 H.sub.7)                                                              oil                                             2.18                                                                              CN     CH(CH.sub.3)CON(C.sub.2 H.sub.5).sub.2                                                           oil                                             2.19                                                                              CN     CH.sub.2COO(isoC.sub.3 H.sub.7)                                                                  oil                                               2.20                                                                            CN                                                                                    ##STR37##                                                           2.21                                                                            CN     CONHCH.sub.3                                                       2.22                                                                              Cl     CH.sub.2CN         viscous                                         2.23                                                                              Cl     CH.sub.2CONH.sub.2 oil                                             2.24                                                                              Cl     C.sub.2 H.sub.5                                                    2.25                                                                              Br     CH.sub.2COOtert.C.sub.4 H.sub.9                                    2.26                                                                              Cl     CH(CH.sub.3)COOCH.sub.3                                            2.27                                                                              COCH.sub.3                                                                           CH.sub.2CN         oil                                             2.28                                                                              COCH.sub.3                                                                           CH.sub.2CONH.sub.2 oil                                             2.29                                                                              COCH.sub.3                                                                           CH.sub.2COOCH.sub.3                                                  2.30                                                                            COCH.sub.3                                                                            ##STR38##                                                           2.31                                                                            COCH.sub.3                                                                           CH.sub.2C CH                                                       2.32                                                                              COCH.sub.3                                                                           CH.sub.3           oil                                             2.33                                                                              COOCH.sub.3                                                                          CH.sub.2CN         oil                                             2.34                                                                              COOCH.sub.3                                                                          CH.sub.2CONH.sub.2                                                 2.35                                                                              C.sub.2 H.sub.5                                                                      CH.sub.2CN                                                         2.36                                                                              CONH.sub.2                                                                           CH.sub.2CONH.sub.2                                                   2.37                                                                            CH.sub.3                                                                              ##STR39##         oil                                               2.38                                                                            Cl                                                                                    ##STR40##                                                           2.39                                                                            CN     CH.sub.2CHCHCH.sub.3                                                                             oil                                             2.40                                                                              CN     CH.sub.2CONHCH.sub.3                                                                             oil                                             2.41                                                                              CN     CH.sub.2CON(CH.sub.3).sub.2                                                                      oil                                             2.42                                                                              CN     CH.sub.2CONHCH.sub.2CHCH.sub.2                                                                   oil                                             2.43                                                                              Cl     CH.sub.2CONHCH.sub.2CCH                                                                          oil                                             2.44                                                                              Cl     CH.sub.2CONHCH.sub.3                                                                             oil                                             2.45                                                                              COCH.sub.3                                                                           CH.sub.2CONHCH.sub.3                                                                             oil                                             2.46                                                                              COCH.sub.3                                                                           CH.sub.2CON(CH.sub.3) C.sub.2 H.sub.5                                                            oil                                             2.47                                                                              COOCH.sub.3                                                                          CH.sub.2CONHCH.sub.3                                                                             oil                                             2.48                                                                              COOCH.sub.3                                                                          CH.sub.2COOCH.sub.3                                                                              oil                                             2.49                                                                              COOCH.sub.3                                                                          CH.sub.2CCH        oil                                             2.50                                                                              NO.sub.2                                                                             CH.sub.2CN         oil                                             2.51                                                                              NO.sub.2                                                                             CH.sub.2CONH.sub.2 oil                                             __________________________________________________________________________

Also the following groups of heterocyclic oxime derivatives are obtainedin an analogous manner.

    ______________________________________                                         ##STR41##                                                                      Comp.                                                                       No.                                                                             R.sub.4 X       Z     Q                                                     ______________________________________                                        3.1   H       CN      S   CH.sub.2CNoil                                       3.2   H       CN      S   CH.sub.2CONH.sub.2                                  3.3   H       CN      S   CH.sub.2COOCH.sub.3                                 3.4   H       CN      S   CH(CH.sub.3)COOCH.sub.3                             3.5   5-Cl    CN      S   CH.sub.2CN                                          3.6   5-Cl    CN      S   CH.sub.2CONH.sub.2                                  3.7   5-Cl    CN      S   CH.sub.2COOC.sub.2 H.sub.5                          3.8   5-Cl    CN      S   CH(CH.sub.3)COOCH.sub.3                             3.9   5-Cl    CN      S   CH(CH.sub.3)COO(isoC.sub.3 H.sub.7)                 3.10  5-Cl    CN      S   CH.sub.2CCH                                         3.11  H       CN      S   CH.sub.2CHCH.sub.2                                  3.12  H       CN      S   CH.sub.2COO(isoC.sub.3 H.sub.7)                     3.13  H       CN      S   C.sub.2 H.sub.5                                     3.14  H       CN      S   CH.sub.2CH.sub.2OCH.sub.3                           3.15  H       CH.sub.3                                                                              S   CH.sub.2CN                                          3.16  H       CH.sub.3                                                                              S   CH.sub.2CONH.sub.2                                  3.17  H       CH.sub.3                                                                              S   CH.sub.2COOCH.sub.3                                 3.18  H       CH.sub.3                                                                              S   CH(CH.sub.3)COOCH.sub.3                             3.19  H       CH.sub.3                                                                              S   CH.sub.2CCHoil                                      3.20  H       CH.sub.3                                                                              S   CH.sub.2CHCH.sub.2                                  3.21  H       CH.sub.3                                                                              S   CH.sub.2COO(isoC.sub.3 H.sub.7)                     3.22  H       CH.sub.3                                                                              S   C.sub.2 H.sub.5                                     3.23  H       CH.sub.3                                                                              S   CH.sub.2CH.sub.2OCH.sub.3                           3.24  H       CN      O   CH.sub.2CNoil                                       3.25  H       CN      O   CH.sub.2CONH.sub.2 vis-                                                       cous                                                3.26  H       CN      O   CH.sub.2COOCH.sub.3                                 3.27  H       CN      O   nC.sub.3 H.sub.7                                    3.28  H       CN      O   CH.sub.2CHCH.sub.2                                  3.29  H       CN      O   CH.sub.2C CH                                        3.30  H       CN      O   CH.sub.2CH.sub.2OCH.sub.3                           3.31  H       CN      O   CONHCH.sub.3 oil                                    3.32  H       CN      O   CONHCH.sub.2CCH solid                                 3.33                                                                              H       CN      O                                                                                  ##STR42##                                            3.34                                                                              5-NO.sub.2                                                                            CN      O   CH.sub.2CNoil                                       3.35  5-Cl    CN      O   CH.sub.2CNoil                                       3.36  H       CH.sub.3                                                                              O   CH.sub.2CNoil                                       3.37  H       CH.sub.3                                                                              O   CH.sub.2CONH.sub.2 oil                              3.38  H       CH.sub.3                                                                              O   CH.sub.2COO(iC.sub.3 H.sub.7)                       3.39  H       NO.sub.2                                                                              O   CH.sub.2CNoil                                       3.40  H       Cl      O   CH.sub.2CNoil                                       3.41  H       Cl      O   CH.sub.2CONH.sub.2 oil                              3.42  H       Cl      S   CH.sub.2CNoil                                       3.43  H       Cl      S   CH.sub.2CONH.sub.2 oil                              3.44  4-CH.sub.3                                                                            CH.sub.3                                                                              O   CH(CH.sub.3)COOCH.sub.3                             ______________________________________                                    

    __________________________________________________________________________     ##STR43##                                                                    Comp.                                                                         No. R.sub.4                                                                           R.sub.5                                                                          X      Z Q                                                         __________________________________________________________________________    3.45                                                                              H   H  CN     S CH.sub.2CN    oil                                         3.46                                                                              H   H  CN     S CH.sub.2CONH.sub.2                                                                          oil                                         3.47                                                                              H   H  CN     S CH.sub.2COOCH.sub.3                                       3.48                                                                              H   H  CN     S C.sub.2 H.sub.5                                           3.49                                                                              H   H  CN     S COC.sub.2 H.sub.5                                         3.50                                                                              H   H  CN     S SO.sub.2CH.sub.3                                            3.51                                                                            H   H  CN     S                                                                                ##STR44##                                                  3.52                                                                            H   H  CN     S CH.sub.2CON(C.sub.3 H.sub.7).sub.2                                                          solid                                       3.53                                                                              2-Cl                                                                              5-Cl                                                                             CN     S CH.sub.2CN    oil                                         3.54                                                                              2-Cl                                                                              5-Cl                                                                             CN     S CH.sub.2CONH.sub.2                                                                          oil                                         3.55                                                                              5-NO.sub.2                                                                        H  CN     O CH.sub.2CN    oil                                         3.56                                                                              H   H  CH.sub.3                                                                             O CH.sub.2CN    oil                                           3.57                                                                            H   H  CH.sub.3                                                                             O                                                                                ##STR45##    solid                                         3.58                                                                            H   H  COCH.sub.3                                                                           O CH.sub.2COOCH.sub.3                                       3.59                                                                              H   H  COCH.sub.3                                                                           O CH(CH.sub.3)COOCH.sub.3                                   3.60                                                                              H   H  NO.sub.2                                                                             O SO.sub.2CH.sub.3                                          3.61                                                                              H   H  Cl     O CH.sub.2CN    oil                                         3.62                                                                              H   H  Cl     O CH.sub.2CONH.sub.2                                                                          oil                                         3.63                                                                              H   H  Cl     O CH.sub.2CONHC.sub.2 H.sub.5                                                                 solid                                       3.64                                                                              H   H  Cl     S CH.sub.2CN    oil                                         3.65                                                                              H   H  CONH.sub.2                                                                           O CH.sub.2CONH.sub.2                                                                          oil                                         3.66                                                                              H   H  COOCH.sub.3                                                                          O CH.sub.2COOCH.sub.3                                                                         oil                                         __________________________________________________________________________

A further important individual group having an action influencing plantgrowth and protecting plants is that of the following diphenyl etherderivatives of the formula:

    ______________________________________                                         ##STR46##                                                                      Comp.                                                                       No.                                                                             X          Q                                                                ______________________________________                                        4.1      CN           CH.sub.2CN                                              4.2      CN           CH.sub.2CONH.sub.2                                      4.3      CN           CH.sub.2COOCH.sub.3                                     4.4      CN           CH(CH.sub.3)COOCH.sub.3                                 4.5      CN           CH(CH.sub.3)COOC.sub.2 H.sub.5                          4.6      CN           CH.sub.3                                                4.7      H            CH.sub.2CN                                              4.8      H            CH.sub.2CONH.sub.2                                      4.9      H            CH.sub.2COOCH.sub.3                                     4.10     CH.sub.3     CH.sub.2CN                                              4.11     CH.sub.3     CH(CH.sub.3)COOCH.sub.3                                 4.12     C.sub.2 H.sub.5                                                                            CH.sub.2COOC.sub.2 H.sub.5                              4.13     Cl           CH.sub.2CN                                              4.14     Cl           CH.sub.2CONH.sub.2                                      4.15     Cl           C.sub.2 H.sub.5                                         4.16     Cl           CH.sub.2CHCH.sub.2                                      4.17     NO.sub.2     CH.sub.2CN                                              4.18     NO.sub.2     CH.sub.2CCH                                             4.19     NO.sub.2     CO NHCH.sub.3                                           4.20     COCH.sub.3   CH.sub.2COO(isoC.sub.3 H.sub.7)                           4.21   COCH.sub.3                                                                                  ##STR47##                                                4.22   COCH.sub.3   CH.sub.2CONH.sub.2                                      4.23     CN           CH.sub.2CONHCH.sub.3                                    4.24     CONH.sub.2   CH.sub.2CONH.sub.2                                      4.25     COOCH.sub.3  CH.sub.2CN                                              4.26     COOCH.sub.3  CH.sub.2COOC.sub.2 H.sub.5                              4.27     COOCH.sub.3  C.sub.2 H.sub.5                                         4.28     COOCH.sub.3  CH.sub.2CCH                                             ______________________________________                                    

A group of compounds which in the case of high applied amounts of 6 kgper hectare and more can shift the plant-growth regulating action in thedirection of a herbicidal action, but which in low applied amounts of 1kg per hectare (and below) are completely tolerated by the crops,without the said compounds losing their properties for regulating plantgrowth and for protecting plants, is that of the following substituteddiphenyl ether derivatives of the formula I:

    ______________________________________                                         ##STR48##                                                                      Comp.                                                                       No.                                                                             R.sub.22 R.sub.23                                                                              X     Q                                                    ______________________________________                                        5.1    4-Cl    2-Cl    CN     CH.sub.2CONH.sub.2                              5.2    4-Cl    2-Cl    CN     CH.sub.2COOCH.sub.3                             5.3    4-Cl    2-Cl    CN     CH(CH.sub.3)COOCH.sub.3                         5.4    4-Cl    2-CN    CN     CH.sub.2COOCH.sub.3                             5.5    4-Cl    2-CN    CN     CH(CH.sub.3)COOCH.sub.3                         5.6    4-CF.sub.3                                                                            2-Cl    CN     CH(CH.sub.3)COOCH.sub.3                         5.7    4-CF.sub.3                                                                            2-Cl    CN     CH.sub.2COOC.sub.2 H.sub.5                      5.8    4-NO.sub.2                                                                            H       CN     CH(CH.sub.3)COOCH.sub.3                         5.9    4-Cl    2-Cl    Cl     CH.sub.2CN                                      5.10   4-Cl    2-Cl    Cl     CH.sub.2COOCH.sub.3                             5.11   4-Cl    2-Cl    Cl     CH(CH.sub.3)COOCH.sub.3                         5.12   4-Cl    2-Cl    CH.sub.3                                                                             CH.sub.2COOCH.sub.3                             5.13   4-Cl    2-Cl    CH.sub.3                                                                             CH(CH.sub.3 )COOCH.sub.3                        5.14   4-Cl    2-Cl    H      CH.sub.2COOCH.sub.3                             5.15   4-Cl    2-Cl    H      CH(CH.sub.3)COOCH.sub.3                         5.16   4-CF.sub.3                                                                            2-Cl    H      CH.sub.2COOCH.sub.3                             5.17   4-CF.sub.3                                                                            2-Cl    H      CH(CH.sub.3)COOCH.sub.3)                        ______________________________________                                    

The compounds of the formula I can be used on their own or together withthe active substances to be antagonised, and also together with suitablecarriers and/or other additives. Suitable carriers and additives can besolid or liquid and they correspond to the substances common informulation practice, such as natural or regenerated mineral substances,solvents, dispersing agents, wetting agents, adhesives, thickeners,binders and/or fertilisers.

The content of active substance in commercial compositions is between0.01 and 90%.

For application, the compounds of the formula I can be in the followingforms (the weight-percentage figures in brackets signify advantageousamounts of active substance):

solid preparations:

dusts and scattering agents (up to 10%), granulates [coated granules,impregnated granules and homogeneous granules] and pellets (1 to 80%);

liquid preparations:

(a) water-dispersible concentrates of active substance:

wettable powders and pastes (25 to 90% in the commercial packing, 0.01to 15% in ready-for-use solutions);

emulsion concentrates and solution concentrates 10 to 50%, 0.01 to 15%in ready-for-use solutions);

(b) solutions (0.1 to 20%), e.g. for dressing, aerosols.

The active substances of the formula I of the present invention can beformulated for example as follows.

Dust: The following substances are used to produce (a) a 5% dust and (b)a 2% dust:

(a)

5 parts of active substance,

95 parts of talcum;

(b)

2 parts of active substance,

1 part of highly dispersed silicic acid, and

97 parts of talcum.

The active substances are mixed and ground with the carriers, and inthis form they can be applied by dusting.

Granulate: The following substances are used to produce a 5% granulate:

5 parts of active substance,

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether,

3.50 parts of polyethylene glycol, and

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved in 6parts of acetone; the polyethylene glycol and cetyl polyglycol ether arethen added. The solution thus obtained is sprayed onto kaolin, and theacetone is subsequently evaporated off in vacuo. A microgranulate ofthis kind can be advantageously worked into seed furrows.

Wettable powder: The following constituents are used to produce (a) a70% wettable powder, (b) a 40% wettable powder, (c) and (d) a 25%wettable powder, and (e) a 10% wettable powder:

(a)

70 parts of active substance,

5 parts of sodium dibutylnaphthylsulphonate,

3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehydecondensate 3:2:1,

10 parts of kaolin, and

12 parts of Champagne chalk;

(b)

40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutylnaphthalenesulphonate, and

54 parts of silicic acid;

(c)

25 parts of active substance,

4.5 parts of calcium lignin sulphonate,

1.9 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1),

1.5 parts of sodium dibutylnaphthalenesulphonate,

19.5 parts of silicic acid,

19.5 parts of Champagne chalk, and

28.1 parts of kaolin;

(d)

25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,

1.7 parts of Champagne chalk/hydroxyethylcellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr, and

46 parts of kaolin; and

(e)

10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates,

5 parts of naphthalenesulphonic acid/formaldehyde condensate, and

82 parts of kaolin.

The active substances are intimately mixed in suitable mixers with theadditives, and the mixture is then ground in the appropriate mills androllers. There are obtained wettable powders which have excellentwetting and suspension properties, which can be diluted with water togive suspensions of the desired concentration, and which can be used inparticular for leaf application, for seed dressing or for the immersiontreatment of seedlings

Emulsifiable concentrate: The following substances are used to produce a25% emulsifiable concentrate:

25 parts of active substance,

2.5 parts of epoxidised vegetable oil,

10 parts of an alkylarylsulphonate/fatty alcohol polyglycol ethermixture,

5 parts of dimethylformamide, and 57.5 parts of xylene.

Emulsions of the desired concentration can be prepared from theseconcentrates by dilution with water; and these emulsions areparticularly suitable for seed dressing.

BIOLOGICAL EXAMPLES

In order to determine the selective herbicidal action of a highlyeffective herbicidal leading product of the chloroacetanilidine class,on its own and together with the antidote of the formula I according tothe invention, the following tests were carried out; the herbicidalactive substance used in the tests wasN-[3'-methoxypropyl-(2')]-2-methyl-6-ethyl-chloroacetanilide (substanceH) (German Offenlegungsschrift No. 2,328,340).

(1) Pre-emergence application as a tank mixture

(a) After sowing

Aqueous suspensions were produced from formulated wettable powders ofthe herbicide (substance H) and from an antidote of the formula I(substance S) according to the invention; and these were then applied,singly and also as mixtures in amounts of 1 kg to 8 kg/hectare withmixture ratios H:S of 4:1 to 1:4, after the sowing of various varietiesof cultivated millet of the Sorghum hybridum type (varieties "Funk","Dekalb", "NK 222" and "DC 59"), in pots or in seed trays in agreenhouse, the said suspensions being applied to the surface of thefoil in the sown vessels. The vessels were then kept at 22°-23° C. withcustomary watering. The results were evaluated after 15 days on thebasis of the following linear scale:

9=plants undamaged (as untreated control plants)

1=plants completely destroyed,

2 to 8=intermediate stages of damage.

(b) Before sowing (PPI)

In the same manner as under (a), soil in pots and in seed trays wastreated with the liquors containing the active substance, andimmediately afterwards these vessels were sown with seeds of the milletvariety "Funk".

Whereas the compound H when used alone in the given applied amountsdamages or destroys the cultivated millet, its effect when an antidoteof the formula I is present is neutralised either completely or to agreat extent. This is achieved in particular with the compounds Nos.1.1, 1.4, 1.14, 1.20 and 1.34.

(2) Seed dressing (wet)

Aqueous emulsion concentrates of an antidote of the formula I wereprepared, and each shaken in a bottle with 50 g of cultivated milletseed. The various concentrations of antidote amounted to between 20 and150 g of antidote per 100 kg of seed. Shortly after the dressingtreatment, the seed was sown in seed trays and treated in the customarymanner with spray liquors of the herbicide H as described under (1a).The results were evaluated 15 days after application of the herbicideusing the same ratings as before.

The results showed here too that protection of the cultivated millet isobtained where the concentration of herbicide is low, but sufficientlyhigh to combat weeds, as a consequence of the antidote S. The followingcompounds were particularly effective as antidotes: Nos. 1.1, 1.4, 1.14,1.20, 1.34, 1.44, 1.70 to 1.75, 1.78, 1.82, 1.88, 1.91, 1.98, 1.103,1.108, 1.110, 1.126, 1.139, 1.173, 1.174, 1.177, 1.188, 1.191, 1.199,1.204, 1.207 to 1.209, 1.217, 1.218, 1.227, 1.230, 1.239, 1.240, 1.253,1.255, 1.267, 1.274, 1.275 to 1.279, and others. Compounds of the U.S.Pat. No. 3,799,757 did not act as antidotes.

The antagonistic action of an antidote of the formula I does not extendas a rule to the main weeds, such as Echinochloa, Setaria italica, etc.,which are destroyed practically to the same extent as they are when theantidote is not present.

Similarly good antidote effects are achieved also with otherchloroacetanilides and thiolcarbamates, and also on other cultivatedcrops, such as rice, maize, wheat, cotton, soya bean or sugar cane.

Increase in yield of soya bean crops

In a field of soya bean plants of the "Lee 68" variety, plots each 50square meters in size were sprayed with aqueous preparations of anactive substance of the formula I when the plants were in the 5-6-leafstage. The amount of active substance applied was 500 g per hectare. Atthe point of time of harvesting, it was established that untreatedplants were for the most part broken (flattened), whilst on the treatedplots all the plants were standing upright and displaying better podsetting. Compared with the control plots, the treated plots gaveapproximately 10-15% higher yields.

Significant increases in yield of 12% or more were achieved on plotswhich had been treated with the compounds Nos. 1.1, 1.3, 1.4, 1.167, orothers.

Reduction of side shoots on tobacco crops

Tobacco plants were grown in a greenhouse and topped as blossoming wasbeginning. One day later they were sprayed with aqueous spray liquors ofthe active substances Nos. 1.106 and 1.148. The concentration of theactive substances was 0.66 and 1.32% of active substance, respectively.

Whereas in the case of the untreated plants, strong side shootsdeveloped from the leaf axil buds, the growth of side shoots on thetreated tobacco plants remained greatly reduced. Similar results wereobtained with other compounds of the formula I with a propargyl etherstructure.

Biological tests under stress conditions

(A) Plant growth at below optimum temperature

Rice plants in the 2- to 3-leaf stage were immersed with the roots andthe lower part of the shoot for 45 minutes in a solution containing 10ppm (=0.001%) of an active substance of the formula I. They wereafterwards replanted in dripping wet soil in asbestos cement containers70×70 cm in size, and kept at a temperature of only 18°-22° C. insteadof at 28°-30° C. The surface of the soil in the containers was coveredwith 2-3 cm of water after 3 days. After a further 18 days, the treatedplants were compared with the untreated control plants.

The rice plants treated with compounds of the formula I or Ia had a rootsystem which was on average 30 to 50% larger. Compounds of the U.S. Pat.No. 3,799,757 showed no such action.

(B) Plant development with slightly damaged seedlings

Rice seed which had been pre-germinated in a quartz sand nutrientsolution was immersed with the formed slightly yellowish shoots for 45minutes in a solution containing 10 ppm of an active substance of theformula I; they were then replanted, with 42 plants in each case, in anasbestos cement vessel as described under A, and subsequently kept,until the time for gathering, at the normal temperature of 28°-30° C.with the customary watering.

The final evaluation was with respect to dry weight of the parts of theplants above the soil, number of panicles and the dry grain weightcompared with 42 correspondingly pre-germinated but untreated controlplants. The following mean values were obtained from several testseries.

    ______________________________________                                                  Control                                                                       plants Treated plants                                                                            Increase                                         ______________________________________                                        dry weight: 507 g    762-820 g   50.3 to 61.7%                                number of panicles:                                                                       242      284-352 g   17.4 to 45.5%                                dry grain weight:                                                                         182 g    220-290 g   20.9 to 59.3%                                ______________________________________                                    

The compounds Nos. 1.1, 1.4, 1.35, 1.44, 1.49, 1.78, 1.88, 1.173, 1.174,1.207, 1.208, 1.217, 1.218, 1.253, 1.276, 1.277, 1.278, 2.1 and 3.1 weredistinguished in this series of tests by particularly high increases.Compounds from U.S. Pat. No. 3,799,757 produced no such effects. Theseeds of other cultivated plants, such as maize, cereals, soya bean andcotton, can be pretreated in a manner analogous to that described in thecase of rice, and similar increases in yield are obtained.

I claim:
 1. A compound of the formula ##STR49## wherein R₁ is hydrogen,halogen or nitro,R₂ is hydrogen or halogen, X is --COOCH₃, --COOC₂ H₅,--CONH₂ or --CONHCH₃, n is the integer 1 or 2, and R₉ is hydrogen ormethyl.
 2. A compound according to claim 1 in which,X is --COOCH₃,--COOC₂ H₅ or --CONHCH₃.
 3. The compound according to claim 2 which is##STR50##